EP1201788B1 - Wärmetauscher aus aluminiumlegierung - Google Patents

Wärmetauscher aus aluminiumlegierung

Info

Publication number
EP1201788B1
EP1201788B1 EP00935514A EP00935514A EP1201788B1 EP 1201788 B1 EP1201788 B1 EP 1201788B1 EP 00935514 A EP00935514 A EP 00935514A EP 00935514 A EP00935514 A EP 00935514A EP 1201788 B1 EP1201788 B1 EP 1201788B1
Authority
EP
European Patent Office
Prior art keywords
vanadium
compound
protective layer
zirconium
aluminum alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00935514A
Other languages
English (en)
French (fr)
Other versions
EP1201788A1 (de
EP1201788A4 (de
Inventor
Toshiyuki Calsonic Kansei Corp. UEHARA
Chizuko Calsonic Kansei Corp. YOSIDA
Etsuko Calsonic Kansei Corp. YAMAZAKI
Kazuya Nihon Parkerizing Co. Ltd. NAKADA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nihon Parkerizing Co Ltd
Marelli Corp
Original Assignee
Calsonic Kansei Corp
Nihon Parkerizing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Calsonic Kansei Corp, Nihon Parkerizing Co Ltd filed Critical Calsonic Kansei Corp
Publication of EP1201788A1 publication Critical patent/EP1201788A1/de
Publication of EP1201788A4 publication Critical patent/EP1201788A4/de
Application granted granted Critical
Publication of EP1201788B1 publication Critical patent/EP1201788B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • F28F19/06—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/084—Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B05D2202/25—Metallic substrate based on light metals based on Al
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • F28F2245/02—Coatings; Surface treatments hydrophilic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • This invention relates to an aluminum alloy thermal exchanger, especially in use for car air-conditioner. It further relates to an aluminum alloy thermal exchanger with film not containing chromium and having excellent corrosion resistance and hydrophile property on the surface of the aluminum alloy.
  • JP63-171684A has disclosed a process to form an anti-corrosive and hydrophilic film on the surface of aluminum alloy by using a synthetic resin of specific monomer. It is, however, unsatisfactory about its hydrophilicity.
  • JP6-116527A has disclosed a process to give a hydrophilicity on aluminum material surface.
  • this method is insufficient to eliminate odor due to its inorganic component.
  • JP1-270977A has disclosed a method to make aluminum alloy of hydrophilic and corrosion resistance. However, it is not desirable to use a film of this method since it contains chromium compound.
  • This invention is provided for resolution of problems against the existing techniques as above mentioned. Namely, it is the purpose of this invention to provide a new aluminum alloy thermal exchanger which has excellent corrosion resistance and hydrophilicity, resolving the problems such as reduction of thermal exchanging efficiency and splash from the condensed water drops, odor exhalation, and of course resolving the problem of harmful chromium.
  • the present inventors found the way of two steps coating on aluminum alloy; the first step is a chemical conversion coating of specific vanadium compound with inorganic zirconium compound, and the second step is an organic-inorganic composite film comprizing specific polyvinyl-alcohol polymer, specific polyoxyethylene glycol, and a mixture of vanadium compound and zirconium compound.
  • the present invention is the aluminum alloy thermal exchanger being characterized in that the aluminum alloy has the first protective layer of chemical conversion coating being produced by using the treatment liquid containing (a) and (b) explained below on the surface of the aluminum alloy, and it further has the second protective layer of hydrophilic film being produced by adding the treatment liquid containing (c), (d), (e), (f) below, and the weight of zirconium in (f) is 40 ⁇ 350 % to the weight of vanadium in (e), and then drying.
  • the Aluminum alloy thermal exchanger of this invention has the first protective layer of a chemical conversion film and the second protective layer of a hydrophilic film on the surface of the aluminum-alloy.
  • the first protective layer is built up on the surface of said aluminumalloy, through chemical conversion treatment using a treatment liquid containing (a) watersoluble vanadium compound and (b) fluorozirconium complex compound.
  • watersoluble vanadium compound (a) it is preferable to apply organic vanadium complex compound being selected from the inorganic vanadium compounds such as metavanadic acid and vanadic acid and their salt of either sodium, potassium, or ammonium, vanadium sulfate, vanadyl sulfate, vanadium nitrate, and vanadium acetate, and also from the organic vanadium complex compounds such as vanadium acetylacetonate, and vanadyl acetylacetonate.
  • organic vanadium complex compound (b) it is more desirable the organic vanadium complex compound.
  • fluorozirconium complex compound (b) it is applicable either zirconium hydrofluoride, zirconium-ammonium fluoride, and zirconium-potassium fluoride.
  • the first protective layer is, as above mentioned, complex chemical conversion film, containing vanadium and zirconium.
  • Fluorozirconium complex compound may be considered to precipitate and to form a framework of oxide or fluoride on the surface of the aluminum alloy, and the frame work may insulate the surface from corrosive matter.
  • white rust resistance is given by zirconium, while the vanadium gives to the aluminum alloy a resistance against pitting corrosion.
  • the first protective layer contributes to an excellent corrosion resistance without chromium.
  • the film weight is preferable at 10 ⁇ 2000 mg/m 2 , and more preferable at 50 ⁇ 500 mg/m 2 .
  • the film weight is preferable at 10 ⁇ 2000 mg/m 2 , and more preferable at 50 ⁇ 500 mg/m 2 .
  • the film weight exceeds 2000 mg/m 2 , it becomes less uniform in film appearance and it arises a bad odor from the second protective layer, so it is better to control the film weight being not more than 2000 mg/m 2 .
  • the vanadium amount in the first protective layer may be preferable at 2 ⁇ 500 mg/m 2 , and more preferable at 10 ⁇ 300 mg/m 2 .
  • the zirconium amount may be preferable at 2 ⁇ 500 mg/m 2 , and more preferable at 10 ⁇ 300 mg/m 2 .
  • corrosion resistance against white rust may become to decrease.
  • each of them become over 500 mg/m 2 , it may become costly and may arise a bad odor.
  • the first protective layer of aluminum/alloy thermal exchanger in this invention is covered by the second protective layer.
  • This second protective layer is built up by using the treatment liquid containing (c),(d),(e) and (f) as explained below.
  • (c) is aqueous polyvinyl alcohol polymer having vinyl-alcohol unit of more than 4 0 mol% and additional polymerization unit (other than the vinyl-alcohol unit of above) of less than 60 mol%.
  • (d) is polyoxyethylene glycol of 6,000 ⁇ 1,000,000 in average molecular weight, (e) is vanadium compound and (f) is zirconium compound And the weight ratio of zirconium in the compound (f) to vanadium in the compound (e) is 40 ⁇ 350 %.
  • Formula (I) below shows example of polyvinyl alcohol polymer (c) explained above, and it may also be another denatured polymer obtainable as reaction product between the polyvinyl-alcohol polymer (I) and diketene.
  • polyvinyl-alcohol polymer shown in formula (I) may include either partial or entire saponificated compounds of poly-vinyl acetate and any copolymers of polyvinyl acetate with other monomer, and there is no limitation to the kind of co-monomer to be copolymerized with vinyl acetate.
  • "X" indicates copolymer being different from vinyl-acetate and vinyl-alcohol and "1", "m", and "n” indicates molecular number of vinyl-alcohol unit, vinyl-acetate unit, and additional polymer unit other than vinyl-acetate, respectively.
  • [ ⁇ n / (1 +m +n) ⁇ x 100] is desirable to be below 40 mole %, and more desirable to be below 30 mole %.
  • [ ⁇ m / (1 +m +n) ⁇ x 100] is desirable to be below 20 mole %, and more desirable to be below 10 mole %. In case of excessive mole ratio of the above, it may reduce water-solubility of the polyvinyl-alcohol.
  • a value of [ ⁇ 1 / (1 +m +n) ⁇ x 100] it may results as 40 ⁇ 100 mole % from both values of above.
  • Hydroxyl group in polyvinyl-alcohol polymer (c) may give to the second protective layer a water-proof property after cross linking reaction with additional copolymer unit and zirconium. And hydroxyl group being not participated such reaction give hydrophile properties to the second protective layer.
  • the average molecular weight is desirable between 6,000 ⁇ 1,000,00 0.
  • the above polyoxyethylene glycol (d) becomes immobilized in the second protective layer by formation of polymeric complex compound with zirconium ion in the zirconium compound (f), and may show odor-preventing properties and hydrophile properties.
  • the average molecular weight of the polyoxyethylene glycol (d) is below 6,000, immobility in the second protective layer may decrease under wet condition, and a durable time of good odor-preventing properties and of good hydrophile properties may decrease. While in case the average molecular weight is over 1,000, 000, it becomes cost up for production of treatment liquid since it becomes difficult itself to dissolve into the water.
  • vanadium compound (e) of the second protective layer in this invention many sort of inorganic and organic vanadium compounds of any vanadium valence may be used, but it is more preferable to use tetravalent or pentavalent vanadium.
  • Inorganic vanadium compounds such as metavanadic acid and vanadic acid and their salt of sodium, potassium, or ammonium, vanadium pentoxide, vanadium sulfate, vanadyl sulfate, vanadium nitrate, vanadyl nitrate, vanadium acetate and vanadium phosphate may be used.
  • organic vanadium compounds such as vanadium acetylacetonate and vanadyl acetylacetonate may be used.
  • Vanadium in the second protective layer shows properties of resisting against pitting corrosion like the vanadium in the first protective layer.
  • the effectiveness of vanadium is deemed with a self-remedy process, which is similar to chromate film.
  • vanadium may move from the film to the corroded portion and may form there a new strong film again and isolate the aluminum alloy from the corrosive matter. It is also deemed that it may produce some compounds in the second protective layer being difficult to dissolve in water, together with zirconium as mentioned later.
  • zirconium compound (f) in the second protective layer in this invention following agent such as zirconium-ammonium carbonate, zirconium-potassium carbonate, zirconyl nitrate, zirconyl sulfate, zirconyl acetate, zircon hydrofluoric acid and its salt may be used.
  • Zirconium in the second protective layer shows white-rust resistant effect similarly to the process of zirconium in the first protective layer by isolating the surface of aluminum alloy from external corrosive matter by formation of framework through cross-linking process between zirconium and hydroxyl group in polyvinyl-alcohol polymer (c).
  • zirconium has a role of building up some water insoluble compound with vanadium, making vanadium difficult to dissolve.
  • For weight ratio of zirconium to vanadium it is preferable between 40 ⁇ 350 %. In case below 40 %, vanadium may decrease its durability time of corrosion resistance. While in case over 350 %, it demerits economically.
  • the polyoxyethylene glycol (d) may be at 1 0 ⁇ 1000 weight ratio
  • vanadium compound (e) may be at 1 ⁇ 200 weight ratio in vanadium-ion
  • zirconium compound (f) may be at 0.4 ⁇ 700 weight ratio in zirconium-ion.
  • the second protective layer in this invention it may include other additives (g), such as anti-microbial agent and mildew-preventing agent, cross-linking agent such as aqueous epoxy resin and surface-active agent in the allowable amount of not impairing the primary effect.
  • Anti-microbial agent and mildew preventing agent which are to be added to prevent foul odor from bacteria's propagation.
  • the decomposition temperature of the anti-microbial agent and mildew-preventing agent is desirable to be at 100°C, and more preferable to be at 150°C in order to keep its effect to the said temperature.
  • the contained weight of the anti-microbial agent and mildew preventing agent is desirable at 0.1 ⁇ 70 wt% to the total weight of (c)+(d) of the second protective layer, and more preferable at 0.3 ⁇ 50 wt % and further more preferable at 0.5 ⁇ 30 wt %. In case below 0.1 wt%, it becomes insufficient on effect, while exceeding 70 wt% it degrades waterproof property of the film.
  • cross linking agent is added in order to make the second protective layer to be a three dimensional structure through reaction with hydroxyl group in polyvinyl alcohol aqueous polymer (c) or with terminal hydroxyl group in polyoxyethylene glycol (d).
  • aldehyde as the cross-linking agent such as polyglycidyl compound, blocking isocyanate, polymethylol compound and glyoxal.
  • These addition of cross linking agent may increase more waterproof properties on the second protective layer.
  • the content of the cross-linking agent is desirable at 0.1 ⁇ 70 wt% to the total content of (c)+(d). In case below 0.1 % wt%, it becomes insufficient the cross-linking effect, while exceeding 70 wt %, it is not desirable for weakening of film adhesion.
  • the content is preferable to be at 0.1 ⁇ 70 wt% to the total content of (c)+(d),and more preferable at 0.3 ⁇ 50 wt %, and further more preferable at 0.5 ⁇ 30 wt%. In case below 0.1 % wt %, it is difficult to obtain a clear effect, while exceeding 70 wt % it degrades the water proof property of the film.
  • the film weight of the second protective layer in this invention may be at 30 ⁇ 5000 mg/m 2 , and more preferable at 40 ⁇ 3500 mg/m 2 , and further more preferable at 50 ⁇ 2500 mg/m 2 .
  • the film weight of the second protective layer in this invention may be at 30 ⁇ 5000 mg/m 2 , and more preferable at 40 ⁇ 3500 mg/m 2 , and further more preferable at 50 ⁇ 2500 mg/m 2 .
  • corrosion resistance, hydrophile properties and odor-preventing properties become insufficient, while exceeding 5000 mg/m 2 may be wasteful.
  • the content of the vanadium compound in the second protective layer may be at 2 ⁇ 500 mg/m 2 being calculated in vanadium element, and more preferable to be at 2 ⁇ 250 mg/m 2 in vanadium element.
  • zirconium compound may preferably be contained at 1 ⁇ 1750 mg/m 2 being calculated in zirconium element, and is more preferable to be 1 ⁇ 875 mg/m 2 , wherein the weight ratio of zirconium to vanadium should be at 40 ⁇ 350 %.
  • the corrosion resistance may be decreased, however when vanadium exceeds 250 mg/m 2 or zirconium exceeds 1750 mg/m 2 , it may be wasteful.
  • the film formation method in this invention First, the surface of the aluminum alloy thermal exchanger is chemically cleaned by using alkali cleaner or acid cleaner. Subsequently, the first protective layer is formed on the surface of the thermal exchanger through chemical conversion coating. And then it is coated with the treatment liquid containing (c) ⁇ (f) and other additives in order to form the second protective layer. Many coating method may be applied, however, it is generally used dipping method. After coating, it is preferable to dry it under a hot blast of 80 ⁇ 250°C and more preferably of 100 ⁇ 200°C.
  • Aluminum alloy thermal exchanger of embodiment examples 1 ⁇ 9 and comparative examples 1 ⁇ 9 were used as specimens. After cleaning the surface, the first protective layer and the second protective layer were farmed. And then tests were carried on the specimens. However, for anti-microbial test, Al-Mn alloy sheets (JIS-A3004) of 70mm ⁇ 150mm ⁇ 1.2mm were used.
  • the treatment solution used in formation of the first protective layer of the embodiment examples are shown in Table 1.
  • the treatment solutions used in formation of the first protective layer of the comparative examples are shown in Table 2. Followings are showing the agent used in (a) -1 ⁇ (a) -3 and (b) -1 ⁇ (b) -2 of Table 1 and 2.
  • the composition of the element in the second protective film are shown in Table 1 and Table 2. The following is the agent used in (c)-1 ⁇ (c) -2 , (d)-1 ⁇ (d)-2, (e)-1 ⁇ (e)-2, (f)-1 ⁇ (f)-3 and (g) of Table 1 and Table 2.
  • the salt spray test according to JID-Z-2371 were carried out for 24 hr, and observed the white rust occurrence at the fin of the thermal exchanger.
  • Test specimens were dipped for 72 hr into a flowing water at room temperature, then the specimens were dried for 1 hr at 80 °C. The specimens were cut into the size of 4 cm ⁇ 4 cm, then nutrient and microbe were sprayed on the cut samples, and then they were cultivated for 14 days at 30 ⁇ 2°C. The number of extracting microbe from the cultivated mat was measured.
  • Microbes Escherichia coli, Bacillus subtilis, Pseudomona aeruginosa
  • the embodiment examples 1 ⁇ 9 of aluminum alloy thermal exchanger having the first protective layer and the second protective layer of this invention showed excellent corrosion resistance as well as excellent hydrophilicity and odor preventive property.
  • the first protective layer and the second protective layer of this invention on the surface of alumin um alloy, it became possible to obtain aluminumalloy thermal exchanger of not containing any harmful chromium ion on its surface and having good corrosion resistance, good hydrophilicity, and excellent preventive capacity against odor for a long term.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (4)

  1. Wärmeaustauscher aus einer Aluminiumlegierung, der folgendes aufweist:
    eine erste Schutzschicht aus einer chemischen Passivierungsschicht, die unter Verwendung von einer die Substanzen (a) und (b) enthaltenden Behandlungsflüssigkeit auf der Oberfläche der Aluminiumlegierung erzeugt worden ist, und ferner
    eine zweite Schutzschicht,
    dadurch gekennzeichnet,
    daß die zweite Schutzschicht aus einer hydrophilen Schicht besteht, die erzeugt wird, indem eine Behandlungsflüssigkeit, die die Substanzen (c), (d), (e) und (f) enthält, wobei das Gewicht von Zirconium in (f) 40 bis 350 Gew.-% des Vanadiums in (e) beträgt, auf die erste Schutzschicht aufgebracht und anschließend getrocknet wird, wobei
    (a) = wasserlösliche Vanadiumverbindung,
    (b) = Fluorzirconium-Komplexverbindung,
    (c) = wäßriges Polyvinylalkoholpolymer, das mehr als 40 Mol-% einer Vinylalkohol-Einheit und weniger als 60 Mol-% einer weiteren Polymerisationseinheit (von der vorstehend angegebenen VinylalkoholEinheit verschieden) aufweist,
    (d) = Polyoxyethylenglycol mit einem durchschnittlichen Molekulargewicht von 60 00 bis 1 000 000,
    (e) = Vananiumverbindung, und
    (f )= Zirconiumverbindung
  2. Wärmeaustauscher aus einer Aluminiumlegierung nach Anspruch 1,
    dadurch gekennzeichnet,
    daß die wasserlösliche Vanadiumverbindung (a) eine oder mehr als eine organische Verbindung aus der Gruppe von Vanadiumacetylacetonat und Vanadylacetylacetonat ist.
  3. Wärmeaustauscher aus einer Aluminiumlegierung nach Anspruch 1,
    dadurch gekennzeichnet,
    daß das Gewicht der ersten Schutzschicht 10 bis 2000 mg/m2, das von Vanadium in der ersten Schutzschicht 2 bis 500 mg/m2 und das von Zirconium in der ersten Schutzschicht 2 bis 500 mg/m2 beträgt.
  4. Wärmeaustauscher aus einer Aluminiumlegierung nach Anspruch 1,
    dadurch gekennzeichnet,
    daß das Gewicht der zweiten Schutzschicht 30 bis 5000 mg/m2, das von Vanadium in der zweiten Schutzschicht 2 bis 500 mg/m2 und das von Zirconium in der zweiten Schutzschicht 1 bis 1750 mg/m2 beträgt.
EP00935514A 1999-06-04 2000-06-01 Wärmetauscher aus aluminiumlegierung Expired - Lifetime EP1201788B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP15783399 1999-06-04
JP15783399A JP4008620B2 (ja) 1999-06-04 1999-06-04 アルミニウム合金製熱交換器
PCT/JP2000/003529 WO2000075397A1 (fr) 1999-06-04 2000-06-01 Echangeur thermique en alliage d'aluminium

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EP1201788A1 EP1201788A1 (de) 2002-05-02
EP1201788A4 EP1201788A4 (de) 2005-06-01
EP1201788B1 true EP1201788B1 (de) 2006-08-16

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EP1201788A1 (de) 2002-05-02
WO2000075397A1 (fr) 2000-12-14
TW452641B (en) 2001-09-01
US6869677B1 (en) 2005-03-22
AU760097B2 (en) 2003-05-08
KR20020013570A (ko) 2002-02-20
KR100706972B1 (ko) 2007-04-13
MY133514A (en) 2007-11-30
CN1353776A (zh) 2002-06-12
EP1201788A4 (de) 2005-06-01
CN1239744C (zh) 2006-02-01
AU5103800A (en) 2000-12-28
BR0011081A (pt) 2002-03-19
JP2000345362A (ja) 2000-12-12
DE60030130D1 (de) 2006-09-28
DE60030130T2 (de) 2007-03-15

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